CN112979945B - All-triazine covalent skeleton and preparation method thereof, and M-N-C prepared based on all-triazine covalent skeleton and method - Google Patents
All-triazine covalent skeleton and preparation method thereof, and M-N-C prepared based on all-triazine covalent skeleton and method Download PDFInfo
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Abstract
The invention discloses an all-triazine covalent skeleton, a preparation method thereof, an M-N-C prepared based on the all-triazine covalent skeleton and a method thereof, belonging to the field of electrocatalysisChemical and fuel cell fields. The invention relates to an all-triazine covalent skeleton and a preparation method thereof, wherein a conductive carbon material, a conductive carbon material and C are added in the polymerization process of the all-triazine covalent skeleton3N3The complete conductive structure is constructed together, so that the material has the capability of rapid electron migration, and the enhanced conductivity can rapidly promote the electron transfer from the electrode to the catalytic site. Furthermore, C3N3Belonging to CTFs, but C3N3The medium N/C ratio (1:1) was much higher than all other reported CTFs. The M-N-C monoatomic catalyst of the invention has higher M-NxIn an amount of, and M-NxMore active sites can be provided for ORR reaction for atomic level dispersion. The preparation method of the invention has the advantages of low preparation cost, high activity of the prepared catalyst and good stability.
Description
Technical Field
The invention belongs to the field of electrocatalysis and fuel cells, and particularly relates to an all-triazine covalent skeleton, a preparation method thereof, an M-N-C prepared based on the all-triazine covalent skeleton and a method thereof.
Background
The PEMFC is a new energy technology which is efficient and clean and directly converts chemical energy of fuel into electric energy, has the advantages of high energy density, quick start, environmental friendliness, quiet work and the like, and has wide application prospects in the fields of electric automobiles, aerospace and the like. However, the high cost and stability problems of PEMFCs are still major bottlenecks that prevent large-scale commercial applications of PEMFCs. The most important is the preparation of the cathode catalyst, mainly because the oxygen reduction (ORR) reaction rate occurring at the cathode is relatively slow, and the platinum-based catalyst is the most excellent at present, but platinum belongs to the precious metal class, and is high in price, extremely low in yield, extremely easy to poison, and severely limits the commercialization of the platinum-based catalyst. Therefore, the selection of materials with low price, high catalytic performance and strong poison resistance is a problem to be solved at present.
Transition Metal-Nitrogen-Carbon (M-N-C, wherein M comprises a transition Metal such as Fe, Co, Mn) type catalyst is currently the most promising non-noble Metal catalyst to replace the noble Metal platinum. However, the carbon skeleton in the precursor is easily decomposed at high temperature (>700 ℃), and clusters or nanoparticles are easily formed during pyrolysis due to the high free energy of the transition metal, so that the M-N-C catalyst has an uneven microstructure, a small number of metal sites and insufficient exposure of active sites.
Covalent triazine backbones (CTFs) have extremely high thermal and chemical stability due to the high nitrogen content enabling the formation of strong covalent bonds. CTFs can be synthesized by different methods and different reaction conditions to control porosity and specific surface area. The nitrogen groups in the CTFs can provide coordination or support for metals, can stabilize metal nanoparticles, and can enable active species to be well dispersed through coordinated or impregnated metal precursors. The retention rate of carbon is improved, and the aggregation of metal atoms in the pyrolysis process is inhibited, so that the metal site density on the carbon material is increased. At the same time, CTFs may offer more possibilities to tune the N composition and M-Nx active species in the final M-N-C catalyst. Despite some reports on ctr based ORR electrocatalysts, CTF materials have not been put to practical use due to the complexity of the manufacturing process, and the complexity, length, and cost of the manufacturing process. At the same time, their electrical conductivity is generally not ideal, which limits their electrochemical applications.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process and low conductivity of an ORR electrocatalyst based on CTFs, and provides an all-triazine covalent skeleton, a preparation method thereof, an M-N-C prepared based on the all-triazine covalent skeleton and a method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for preparing an all-triazine covalent skeleton comprises the following steps:
introducing argon into a 1, 4-dioxane solvent, adding 1,3, 5-triazine and cyanuric chloride into the 1, 4-dioxane solvent, and uniformly dispersing;
wherein, the total mass of 1,3, 5-triazine and cyanuric chloride added in each 60mL of 1, 4-dioxane is 500 mg;
adding an N, N-diisopropylethylamine catalyst and a conductive carbon material into the uniformly dispersed solution, and uniformly mixing to obtain a reaction solution;
carrying out polymerization reaction on the reaction solution at 70-100 ℃ for 8-24 h under the protection of argon;
and after the reaction is finished, carrying out suction filtration, cleaning and drying on the reactant to obtain the all-triazine covalent skeleton.
Further, the mass ratio of the 1,3, 5-triazine and the cyanuric chloride added into the 1, 4-dioxane solvent is (0.5-3): 1.
further, the conductive carbon material is one or more of carbon powder, mesoporous carbon, carbon microspheres, graphene, carbon nanotubes or carbon nanofibers.
Further, the ratio of the added mass of the conductive carbon material to the total mass of the 1,3, 5-triazine and the cyanuric chloride is (0.2-1): 1;
1-3 mL of N, N-diisopropylethylamine catalyst is correspondingly added into every 500mg of 1,3, 5-triazine and cyanuric chloride.
An all-triazine covalent scaffold prepared according to the preparation method of the invention.
The method for preparing the M-N-C monatomic catalyst based on the all-triazine covalent skeleton comprises the following steps:
uniformly mixing the all-triazine covalent skeleton and transition metal salt in water, reacting at 60-90 ℃ for 4-6 h, washing with water and drying to obtain M-C3N3；
Wherein M is a transition metal element in the transition metal salt;
mixing M-C3N3Calcining for 1-3 h at 600-1000 ℃ in a nitrogen environment, and carbonizing;
then removing impurities from the carbonized product by using concentrated acid, cleaning and drying;
putting the dried solid in NH3And (3) carrying out secondary calcination in the environment, and calcining at 650-850 ℃ for 20-60 min to obtain the target product M-N-C.
Further, the transition metal salt is one or more of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and nickel nitrate.
Further, at M-C3N3The mass ratio of the medium M to the total triazine covalent skeleton is (0.1-1): 1.
the M-N-C monatomic catalyst obtained by the preparation method is provided.
Further, the catalyst PEMFC is used in cathode oxygen reduction reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to an all-triazine covalent skeleton and a preparation method thereof, wherein a conductive carbon material is added in the polymerization process of the all-triazine covalent skeleton, and the obtained all-triazine covalent skeleton comprises C3N3And the conductive carbon material jointly construct a complete conductive structure, so that the material has the capability of fast electron migration, and the enhanced conductivity can quickly promote electrons to be transferred from the electrode to a catalytic site. Furthermore, C3N3Belonging to CTFs, but C3N3Has an N/C ratio of 1:1, which is much higher than all other reported CTFs.
The invention relates to a method for preparing an M-N-C monatomic catalyst based on an all-triazine covalent skeleton, which takes the all-triazine covalent skeleton as a raw material, C3N3Compared with other CTFs, the CTFs have more triazine units, the electronegativity and the catalytic activity of the material are expected to be improved, and a plurality of N coordination sites introduce transition metal ions into a carbon-nitrogen skeleton to promote the activity of M-NxThe sites are dispersed and formed, and the metal M is protected to exist in an atomic state in the carbonization process and not to migrate and agglomerate; by carbonizing M-C under Ar atmosphere3N3For increasing the electrical conductivity and catalytic activity of the material, C3N3Conversion to N-doped porous carbon and uniform dispersion of metal atoms; atomic size metals achieve the greatest degree of active center exposure. Then acid leaching and adding NH3Carrying out second heat treatment under the atmosphere to obtain an M-N-C catalyst; in the M-N-C catalyst, metal atoms are uniformly distributed with definite M-N4The coordinated framework has a uniform coordination environment and high atom utilization rate; by NH3The treatment, disordered carbon phase increase and pore volume increase, so that the M-N-C catalyst has larger specific surface area and abundant pore structure, effectively improves the charge transmission efficiency and provides more flexibility for doping M into the structure.
The M-N-C monoatomic catalyst of the invention has higher M-NxIn an amount of, and M-NxMore active sites can be provided for ORR reaction for atomic level dispersion. Therefore, M-N-C monatomic catalyst has excellent ORR activity, and its half-wave potential and initial potential are superior to those of commercial Pt/C catalystAnd also exhibit significant advantages over other non-noble metal catalysts. In addition, M-N-C monatomic catalysts are more stable and more resistant to methanol than commercial Pt/C catalysts. Compared with the expensive preparation cost of a Pt/C catalyst, the M-N-C monatomic catalyst has the advantages of lower preparation cost, simple preparation process and excellent comprehensive performance, thereby showing good potential in the commercial application of PEMFCs.
Drawings
FIG. 1 is a flow chart of the preparation of the Fe-N-C catalyst of example 1;
FIG. 2 is a morphology of the Fe-N-C catalyst of example 1
FIG. 3 is a XANES and Fe K-edge FT-EXAFS test chart of the Fe-N-C catalyst of example 1;
FIG. 4 is a graph of performance tests of the Fe-N-C catalyst and the commercial Pt/C catalyst of example 1, wherein FIG. 4(a) is a linear scan of the Fe-N-C catalyst and the commercial Pt/C catalyst of example 1 in 0.1M KOH; FIG. 4(b) is a chronoamperometric graph of the Fe-N-C catalyst and the commercial Pt/C catalyst of example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
Preparation of Fe-N-C catalyst
Firstly, introducing argon gas for 20min into 60mL of 1, 4-dioxane solvent, adding 250mg of 1,3, 5-triazine and 250mg of cyanuric chloride into the 1, 4-dioxane solvent, and carrying out ultrasonic homogenization; then, 3mL of an N, N-diisopropylethylamine catalyst and 250mg of Keqin carbon were added to obtain a reaction solution; placing the reaction solution in an oil bath at 95 ℃ under the protection of argon to react for 24 hours; after the reaction is finished, filtering the reactant, cleaning the reactant by using 1, 4-dioxane, ethanol and ultrapure water, and drying the reactant to obtain an all-triazine covalent skeleton; reaction formula of all-triazine covalent skeleton referring to fig. 1, the resulting all-triazine covalent skeleton comprises C3N3And Keqin carbon;
100mg of all-triazine covalent backbone and 120mg of FeCl3.6H2Dissolving O in 120mL of ultrapure water, then reacting the solution at 70 ℃ for 4h, washing with water and drying to obtain Fe-C3N3(ii) a Then, Fe-C is added3N3Calcining at 750 deg.C for 2 hr in a tubular furnace at nitrogen atmosphere with a heating rate of 10 deg.C/min-1(ii) a To remove unstable species and exposed metals and metal oxides, the carbonized product was taken at 0.5M H2SO4Soaking in the solution for 12h, washing with a large amount of ultrapure water, filtering, and drying in a vacuum oven; finally in NH3And carrying out secondary calcination (750 ℃ and 1h) in the environment to obtain the target catalyst Fe-N-C. With triazine covalent skeleton C3N3The process to the target catalyst Fe-N-C is shown in FIG. 1.
Referring to fig. 2, fig. 2 is a TEM test chart of Fe-N-C of example 1, and from fig. 2, it can be seen that Fe-N-C is a nanosheet structure, and no obvious Fe nanoparticles or clusters are observed on the surface of the sample, meaning that Fe exists in atomic size, indicating that Fe atoms do not agglomerate seriously during pyrolysis.
Referring to FIG. 3, FIG. 3 is an X-ray absorption fine structure diagram of Fe-N-C of example 1, FIG. 3(a) is a Fe K edge XANES spectrum of Fe-N-C catalyst, the leading edge peak at 7114.7eV is attributable to a dipole-forbidden but quadrupole-allowed 1s → 3d transition, and simultaneous charge transfer of the ligand to the metal, indicating that the predominant coordination geometry around Fe is close to a square structure; this edge front peak is generally considered to be Fe-N4Flat fingerprint peaks. At the absorption edge (. about.7120-7140 eV), the Fe-N-C catalyst exhibits several main characteristic peaks of the 1s → 4p transition, which is characteristic of the iron complex having a square planar configuration. In addition, with Fe (Fe)0)，FeO(Fe2+) And Fe2O3(Fe3+) In contrast, the absorption edge of Fe-N-C is located at Fe0And Fe3+In between, it indicates that the Fe monoatomic atom carries a positive charge and can be anchored by the N atom. FIG. 3(b) is a spectrum of Fe K-edge FT-EXAFS in Fe-N-C at
Showing a main characteristic peak, Fe-N of the first coordination shellxIn connection with this, it is directly shown that Fe-N complexes are formed by the bond between Fe and N atoms. These results confirm that the Fe atoms are anchored by the N atoms and are atomically dispersed, and also do not transform into an inorganic phase after pyrolysis at high temperature, which is consistent with the characterization results of TEM.
Referring to FIG. 4, FIG. 4(a) studies of commercial Pt/C catalyst and Fe-N-C catalyst with LSV at room temperature2Catalytic Activity in saturated 0.1M KOH solution (Scan Rate 5 mV. multidot.s)-1At 1600 rpm). The limiting current of Fe-N-C is 4.75mA cm-2Limiting current (3.8mA cm) superior to commercial Pt/C-2). Fe-N-C has a half-wave potential of 0.840V (vs. RHE) greater than that of commercial Pt/C by 0.832V (vs. RHE), and its initial potential is also greater than that of Pt/C, indicating that Fe-N-C has superior oxygen reduction activity to Pt/C. FIG. 4(b) Long term stability of commercial Pt/C catalyst and Fe-N-C catalyst was studied using chronoamperometry, with the Pt/C catalyst current decreasing by 44% and the Fe-N-C current decaying by about 12% after 28000s of continuous operationThe results show that the stability of Fe-N-C is superior to that of the commercial Pt/C catalyst. FIG. 4 demonstrates the application prospect of the prepared Fe-N-C catalyst as a noble metal catalyst substitute.
Example 2
Preparation of Co-N-C catalyst
Introducing argon into 60mL of 1, 4-dioxane solvent for 20min, then adding 250mg of 1,3, 5-triazine and 125mg of cyanuric chloride into the 1, 4-dioxane solvent, uniformly performing ultrasonic treatment, and adding 3mL of N, N-diisopropylethylamine catalyst and 100mg of carbon nano tube to obtain a reaction solution; placing the reaction solution in an oil bath at 95 ℃ under the protection of argon for reaction for 24 hours, after the reaction is finished, carrying out suction filtration on the reactant, cleaning the reactant with 1, 4-dioxane, ethanol and ultrapure water, and drying the reactant to obtain an all-triazine covalent skeleton;
100mg of the prepared all-triazine covalent skeleton and 60mg of CoCl2.6H2Dissolving O in 120mL of ultrapure water, reacting the solution at 80 ℃ for 4h, washing with water and drying to obtain Co-C3N3(ii) a Mixing Co-C3N3Calcining at 850 deg.C for 2 hr in a tubular furnace at nitrogen atmosphere with a heating rate of 10 deg.C/min-1. To remove unstable species, and exposed metals and metal oxides, the carbonized product was taken at 0.5M H2SO4The solution was soaked for 12h, then washed with copious amounts of ultrapure water, filtered, and dried in a vacuum oven. At NH3And (4) carrying out secondary calcination (650 ℃,1h) in the environment to obtain the target catalyst Co-N-C.
The half-wave potential of Co-N-C was found to be 0.836V (vs. RHE). After 28000s of continuous operation, the current of Co-N-C decayed by about 21%.
Example 3
Preparation of Ni-N-C catalyst
Introducing argon into 60mL of 1, 4-dioxane solvent for 20min, adding 250mg of 1,3, 5-triazine and 100mg of cyanuric chloride into the 1, 4-dioxane solvent, uniformly performing ultrasonic treatment, and adding 5mL of N, N-diisopropylethylamine catalyst and 100mg of graphene to obtain a reaction solution; placing the reaction solution in an oil bath at 75 ℃ under the protection of argon for reaction for 20 hours, after the reaction is finished, carrying out suction filtration on the reactant, cleaning the reactant with 1, 4-dioxane, ethanol and ultrapure water, and drying the reactant to obtain an all-triazine covalent skeleton;
100mg of all-triazine covalent backbone and 40mg of NiCl2.6H2Dissolving O in 120mL of ultrapure water, reacting the solution at 60 ℃ for 4h, washing with water and drying to obtain Ni-C3N3(ii) a Mixing Ni-C3N3Calcining at 950 deg.C for 2h in a tubular furnace under nitrogen atmosphere at a heating rate of 10 deg.C/min-1(ii) a To remove unstable species, and exposed metals and metal oxides, the carbonized product was taken at 0.5M H2SO4Soaking in the solution for 12h, washing with a large amount of ultrapure water, filtering, and drying in a vacuum oven; then at NH3And (4) carrying out secondary calcination (650 ℃,40min) under the environment to obtain the target catalyst Ni-N-C.
The test shows that the half-wave potential of Ni-N-C is 0.834V (vs. RHE). After 28000s of continuous operation, the current of Co-N-C decayed by about 42%.
Example 4
Preparation of Fe, Co-N-C catalyst
Introducing argon into 60mL of 1, 4-dioxane solvent for 20min, adding 125mg of 1,3, 5-triazine and 250mg of cyanuric chloride into the 1, 4-dioxane solvent, uniformly performing ultrasonic treatment, and then adding 5mL of N, N-diisopropylethylamine catalyst and 50mg of graphene to obtain a reaction solution; placing the reaction solution in an oil bath at 85 ℃ for reaction for 14h (under the protection of argon gas); finally, the reactant is filtered, and is dried after being cleaned by 1, 4-dioxane, ethanol and ultrapure water, so as to obtain the all-triazine covalent skeleton;
100mg of all-triazine covalent backbone, 40mg of CoCl2.6H2O and 40mg FeCl3.6H2Dissolving O in 120mL of ultrapure water, reacting the solution at 70 ℃ for 4h, washing with water and drying to obtain Fe, Co-C3N3(ii) a Mixing Fe, Co-C3N3Calcining at 650 deg.C for 2 hr in a tubular furnace at a temperature of 10 deg.C/min under nitrogen atmosphere-1(ii) a To remove unstable species, and exposed metals and metal oxides, the carbonized product was taken at 0.5M H2SO4Soaking in the solution for 12h, washing with a large amount of ultrapure water, and filteringAnd drying in a vacuum oven; finally in NH3And (4) carrying out secondary calcination (850 ℃,20min) under the environment to obtain the target catalyst Fe, Co-N-C.
The half-wave potential of Fe, Co-N-C was found to be 0.841V (vs. RHE) as measured. After 28000s of continuous operation, the current of Co-N-C decayed by about 10%.
Compared with the expensive preparation cost of commercial Pt/C catalysts, the preparation method of the invention has lower preparation cost. The catalyst has high activity, good stability, simple preparation process and excellent comprehensive performance, and provides an effective way for designing a non-platinum catalytic system of a fuel cell.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (5)
1. The method for preparing the M-N-C monatomic catalyst by using the all-triazine covalent skeleton is characterized by comprising the following steps of:
uniformly mixing the all-triazine covalent skeleton and transition metal salt in water, reacting at 60-90 ℃ for 4-6 h, washing with water and drying to obtain M-C3N3；
Wherein M is a transition metal element in the transition metal salt;
mixing M-C3N3Calcining for 1-3 h at 600-1000 ℃ in a nitrogen environment, and carbonizing;
then removing impurities from the carbonized product by using concentrated acid, cleaning and drying;
putting the dried solid in NH3Performing secondary calcination in the environment, and calcining at 650-850 ℃ for 20-60 min to obtain a target product M-N-C;
the all-triazine covalent skeleton is prepared by the following preparation method:
introducing argon into a 1, 4-dioxane solvent, adding 1,3, 5-triazine and cyanuric chloride into the 1, 4-dioxane solvent, and uniformly dispersing;
wherein, the total mass of 1,3, 5-triazine and cyanuric chloride added in each 60mL of 1, 4-dioxane is 500 mg;
adding an N, N-diisopropylethylamine catalyst and a conductive carbon material into the uniformly dispersed solution, and uniformly mixing to obtain a reaction solution;
carrying out polymerization reaction on the reaction solution at 70-100 ℃ for 8-24 h under the protection of argon;
and after the reaction is finished, carrying out suction filtration, cleaning and drying on the reactant to obtain the all-triazine covalent skeleton.
2. The method for preparing an M-N-C monatomic catalyst according to claim 1, wherein the transition metal salt is one or more of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate, nickel nitrate.
3. The method of claim 1, wherein the catalyst is in the form of M-N-C monatomic catalyst3N3The mass ratio of the medium M to the total triazine covalent skeleton is (0.1-1): 1.
4. an M-N-C monatomic catalyst obtained by the production method according to claim 1, 2 or 3.
5. Use of an M-N-C monatomic catalyst according to claim 4, characterized in that said catalyst is used in PEMFC cathodic oxygen reduction reactions.
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| CN102600809A (en) * | 2012-03-16 | 2012-07-25 | 陕西科技大学 | Amino end-group triazine ring tree-shaped macromolecular adsorbent and preparation method thereof |
| CN107129583B (en) * | 2017-05-25 | 2019-11-15 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN110408032B (en) * | 2019-06-28 | 2023-01-03 | 中北大学 | Silsesquioxane modified melamine flame retardant and preparation method thereof |
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